WO1997014395A1

WO1997014395A1 - Aqueous lacquer packaged in an aerosol device and including at least one silicone graft polymer for treating keratinous materials, and uses thereof

Info

Publication number: WO1997014395A1
Application number: PCT/FR1996/001571
Authority: WO
Inventors: Christine Dupuis
Original assignee: L'oreal
Priority date: 1995-10-18
Filing date: 1996-10-08
Publication date: 1997-04-24
Also published as: KR100300215B1; PL186008B1; EP0855897B1; FR2740032B1; FR2740032A1; US6350439B1; RU2152781C1; JPH11500746A; CA2232429A1; EP0855897A1; ATE288734T1; US6440404B1; KR19990064323A; PL326299A1; DE69634337D1; JP3112687B2; DE69634337T2; BR9611018A

Abstract

A composition for treating keratinous materials, particularly human hair, is disclosed. The composition is packaged in an aerosol device and forms a lacquer at the outlet of the device. Said composition contains (a) at least one silicone graft polymer including a polysiloxane portion and a portion consisting of a non-silicone organic chain, where one of said portions forms the main polymeric chain while the other is grafted onto said main chain; (b) at least 30 wt % of water; (c) at least one propellant; and (d) an organic solvent in an amount of 0-25 wt %; the above percentages by weight being based on the total weight of the composition in the aerosol. Such aqueous lacquers are particularly useful for fixing and/or styling and/or conditioning hair.

Description

WATER-BASED LACQUER FOR THE TREATMENT OF KERATINIC MATERIALS,

PACKAGED IN AN AEROSOL DEVICE, INCLUDING

LESS A GRAFT SILICONE POLYMER AND APPLICATIONS

The present invention relates to an aqueous composition for the treatment of keratmic materials, in particular human hair, in the form of a lacquer, packaged in an aerosol device for producing a lacquer, comprising a small amount of organic solvent and at least one silicone polymer. grafted comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer, the other being grafted onto said main chain

In what follows, the term “lacquer” means any composition leaving the outlet of a spraying device in the form of liquid droplets directly sprayed onto the keratinous support.

Polymers of the grafted silicone polymer type comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer the other being grafted onto said main chain are known for their styling properties. They are particularly interesting in hair cosmetics because they provide hold to the hair.

For a certain number of years, a very particular interest has manifested itself for aerosol lacquers as a mode of conditioning formulations for maintaining the hairstyle and / or shaping the hairstyle Aerosol lacquers containing the grafted silicone polymers as described above, are generally alcoholic and more preferably hydroalcoholic and generally contain in addition a surfactant These compositions, containing more than 25% by weight of organic solvent, tend, after deposition of said polymers to lead to phenomena of foam, to confer insufficient shine properties to give not totally sufficient fixing powers and to weigh down the hair (load effects) The Applicant has surprisingly found that the use of a polymer of the grafted silicone polymer type comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer l the other being grafted onto said main chain in an aqueous lacquer, pressurized in an aerosol device, comprising at least 30% by weight of water and at most 25% by weight of organic solvent, after application and drying, made it possible to improve the shine of the hair and to present a better lacquering power. In addition, this use made it possible to significantly reduce or even completely eliminate the loading effects on the hair.

The Applicant has also found that the pressurized aqueous lacquers in accordance with the invention did not lead to foaming phenomena on the hair resulting in a bleaching effect or to dusting or grinding phenomena. They also provide good styling and styling properties. hair styling, good hold on the hair and easy detangling

The aqueous composition, according to the present invention, packaged in an aerosol device and producing at the outlet of the device a lacquer is characterized in that it comprises

(a) at least one grafted silicone polymer comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer, the other being grafted onto said main chain,

(b) at least 30% by weight of water,

(c) at least one propellant,

(d) an amount of organic solvent ranging from 0 to 25% by weight, the percentages by weight being defined relative to the total weight of the composition in the aerosol

The silicone polymers grafted according to the invention are preferably chosen from polymers with a non-silicone organic skeleton grafted with monomers containing a polysiloxane, polymers with a polysiloxane backbone grafted with non-silicone organic monomers and mixtures thereof

In what follows, the term silicone or polysiloxane is intended to denote, in accordance with general acceptance, any organosilicon polymer or oligomer with linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and / or polycondensatioπ of silanes suitably functionalized, and consisting essentially of a repetition of main units in which the silicon atoms are linked together by oxygen atoms (siloxane bond ≡Sι-O-Sι≡), optionally substituted hydrocarbon radicals being directly bonded via a carbon atom on said silicon atoms The most common hydrocarbon radicals are alkyl radicals, in particular C _T -C ₁₀ and in particular methyl, fluoroalkyl radicals, aryl radicals and in particular phenyl, and alkenyl radicals and in particular vinyl, other types of radicals capable of being linked either directly or via a hydrocarbon radical, to the siloxane chain are in particular hydrogen, halogens and in particular chlorine, bromine or fluorine, thiols, alkoxy radicals, polyoxyalkylene radicals (or polyethers) and in particular polyoxyethylene and / or polyoxypropylene, hydroxyl or hydroxyalkyl radicals, substituted or unsubstituted amino groups, amide groups, acyloxy or acyloxyalkyl radicals, hydroxyalkylamino or aminoalkyl radicals, quaternary ammonium groups, amphoteric or betainic groups , anionic groups such as carboxylates, thioglycolates, sulfosuccinates, thiosulfates, phosphates and sulfates, this list being of course in no way limiting (so-called "organomodified" silicones)

In the following, the expression “polysiloxane macromer” is intended to denote, in accordance with general acceptance, any monomer containing in its structure a polymer chain of the polysiloxane type. The polymers with a non-silicone organic skeleton grafted with monomers containing a polysiloxane in accordance with the present invention consist of an organic main chain formed from organic monomers not containing silicone, on which is grafted, inside of said chain as well as optionally at at least one of its ends, at least one polysiloxane macromer.

The non-silicone organic monomers constituting the main chain of the grafted silicone polymer can be chosen from ethylenically unsaturated monomers which can be polymerized by the radical route, monomers which can be polymerized by polycondensation such as those forming polyamides, polyesters, polyurethanes, opening monomers such as those of the oxazoline or caprolactone type.

The polymers with a non-silicone organic skeleton grafted with monomers containing a polysiloxane in accordance with the present invention can be obtained according to any means known to those skilled in the art, in particular by reaction between (i) a starting polysiloxane macromer correctly. functionalized on the polysiloxane chain and (ii) one or more organic silicone compounds, themselves correctly functionalized by a function which is capable of reacting with the functional group or groups carried by said silicone by forming a covalent bond; a classic example of such a reaction is the radical reaction between a vinyl group carried on one of the ends of the silicone with a double bond of an ethylenically unsaturated monomer of the main chain.

The polymers with a non-silicone organic skeleton grafted with monomers containing a polysiloxane, in accordance with the invention, are more preferably chosen from those described in patents US 4,693,935, US 4,728,571 and US 4,972,037 and patent applications EP-A-0412704 , EP-A-0412707, EP-A-0640105 and WO 95/00578. These are copolymers obtained by radical polymerization from ethylenically unsaturated monomers and silicone macromers having a terminal vinyl group or many copolymers obtained by reaction of a polyolefin comprising functionalized groups and of a polysiloxane macromer having a terminal function reactive with said functionalized groups.

A particular family of grafted silicone polymers suitable for carrying out the present invention consists of silicone graft copolymers comprising:

a) from 0 to 98% by weight of at least one lipophilic monomer (A) of low lipophilic polarity with ethylenic unsaturation, polymerizable by the radical route; b) from 0 to 98% by weight of at least one polar hydrophilic ethylenically unsaturated monomer (B), copolymeric with the monomer or monomers of type (A), c) from 0.01 to 50% by weight of minus one polysiloxane macromer (C) of general formula:

or

X denotes a vinyl group copolymeric with the monomers (A) and

(B), Y denotes a divalent linking group,

R denotes hydrogen, Cι-C ₆ alkyl or alkoxy, C ₆ -Cι ₂ aryl;

Z denotes a monovalent polysiloxane unit having a number average molecular weight of at least 500; n is 0 or 1 and m is an integer ranging from 1 to 3, the percentages being calculated relative to the total weight of the monomers (A), (B) and (C).

These polymers are described as well as their preparation processes in US patents 4,693,935, US 4,728,571 and US 4,972,037 and patent applications EP-A-0412704, EP-A-0412707, EP-A-0640105. They have a number average molecular weight preferably ranging from 10,000 to 2,000,000 and preferably a glass transition temperature Tg or a crystalline melting temperature Tm of at least -20 ° C. Examples of lipophilic monomers (A) that may be mentioned are acrylic or methacrylic acid esters of Crdβ alcohols, styrene, polystyrene macromers, vinyl acetate, vinyl propionate, alpha-methyl- styrene, tert-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene, esters of acrylic or methacrylic acid and

1, 1 -dιhydro-perfluoroalcanol or its counterparts, esters of acrylic or methacrylic acid and omega-hydrydofluroalcanol, esters of acrylic or methacrylic acid and fluoroalkylsulfoamido-alcohol, esters of acrylic or methacrylic acid and d fluoroalkyl alcohol, esters of acrylic or methacrylic acid and alcohol fluroether, or mixtures thereof

The preferred monomers (A) are chosen from the group consisting of n-butyl methacrylate, isobutyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-ethylhexyl methacrylate, methacrylate methyl, 2- (N-methyl perflurooctane sulfonamido) - ethylacrylate, 2- (N-butylperflurooctane sulfoπamιdo) -ethylacrylate and mixtures thereof

Examples of polar monomers (B) that may be mentioned are acrylic acid, methacrylic acid, N, N-methylacrylamide, dimethylaminoethyl methacrylate, dimethylaminoethyl quaternized methacrylate, (meth) acrylamide, Nt -butylacrylamide, maleic acid, maleic anhydride and their half-esters, hydroxyalkylated (meth) acrylates, diallyl-dimethylammomum chloride, vinylpyrrolidone, vinyl ethers, maleimides, vinylpyπdine, vinyhmidazole, polar heterocyclic vinyl compounds, styrene sulfonate, allylic alcohol, vinyl alcohol, vinylcaprolactam or mixtures thereof The preferred monomers (B) are chosen from the group consisting of acrylic acid, N, N-dιmethylacrylamide , dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinylpyrrolidone and mixtures thereof The preferred polysiloxane macromers (C) of formula (I) are chosen from those corresponding to the following general formula (II): o ÇH ₃

1 2 "3 I

CHR ¹ = CR ² - CO (CH ₂ ) _q (O) - Si (R ³ ) ₃ - ^ - (-O - Si -) - R ⁴

CH ₃ (II) in which: R ¹ is hydrogen or -COOH (preferably hydrogen);

R ² is hydrogen, methyl or -CH ₂ COOH (preferably methyl); R ³ is Cι-C _6l alkyl, alkoxy or alkylamino C ₆ -Cι ₂ aryl or hydroxyl (preferably methyl);

R ⁴ is Cι-C ₆ alkyl, alkoxy or alkylamino, C ₆ -C ₁₂ aryl or hydroxyl (preferably methyl); q is an integer from 2 to 6 (preferably 3); p is 0 or 1; r is an integer from 5 to 700; m is an integer ranging from 1 to 3 (preferably 1).

More particularly, the polysiloxane macromers of formula

O I I CH, CH CH,

CH, = CC- O— (CH ₂ ) ₃ - Si - O-hSi-Of-Si - (ChL 2b'3-CH,

CH ₃ CH ₃ CH, CH ₃ n with n being a number ranging from 5 to 700.

A particular embodiment of the invention consists in using a copolymer capable of being obtained by radical polymerization from the mixture of monomers consisting of: a) 60% by weight of tert-butyl acrylate; b) 20% by weight of acrylic acid; c) 20% by weight of silicone macromer of formula: O CH, CH, CH, i ³ i ³

CH, = C-C-0 - (CHA -Si - O -Sι-0 Si - (CH,)., - CH

CH, CH, CH, CH- n with n being a number ranging from 5 to 700, the percentages by weight being calculated relative to the total weight of the monomers

Another particular embodiment of the invention consists in using a copolymer capable of being obtained by radical polymerization from the mixture of monomers consisting of a) 80% by weight of tert-butyl acrylate, b) 20% by weight of silicone macromer of formula

O CH, CH, CH-

CH = CC-0 - (CH,), - Si - θ4-Si-0 ^• Si - (CH ₂ ) ₃ - CH,

CH, CH, CH, CH, n with n being a number ranging from 5 to 700, the percentages by weight being calculated relative to the total weight of the monomers

Another particular family of silicone polymers suitable for carrying out the present invention consists of silicone graft copolymers capable of being obtained by reactive extrusion of a polysiloxane macromer having a terminal reactive function on a polymer of the polyolefin type comprising reactive groups capable of reacting with the terminal function of the polysiloxane macromer to form a covalent bond allowing the grafting of the silicone onto the main chain of the polyolefin

These polymers are described as well as their preparation process in patent application WO 95/00578 The reactive polyolefins are preferably chosen from polyethylenes or polymers of monomers derived from ethylene such as propylene, styrene, alkylstyrene, butylene, butadiene, (meth) acrylates, vinyl esters or the like, comprising reactive functions capable of to react with the terminal function of the polysiloxane macromer They are chosen more particularly from copolymers of ethylene or of derivatives of ethylene and of monomers chosen from those comprising a carboxylic function such as (meth) acrylic acid, those comprising a function acid anhydride such as maleic acid anhydride, those comprising an acid chloride function such as (meth) acrylic acid chloride, those comprising an ester function such as acid esters ( meth) acrylic, those comprising an isocyanate function

The silicone macromers are preferably chosen from polysiloxaπes comprising a functionalized group, at the end of the polysiloxane chain or near the end of said chain, chosen from the group consisting of alcohols, thiols, epoxy, primary amines and secondary and more particularly among those corresponding to the general formula (III)

T- (CH ₂ ) _s -Sι - [- (OSιR ⁵ R ⁶ ) _t -R ⁷ ] _y (III) in which T is chosen from the group consisting of NH2, NHR ', an epoxy function, OH, SH, R ⁵ , R ⁶ , R ⁷ and R ', independently, denote a Cι-C ₅ alkyl, phenyl, benzyl, or C ₆ -C ₁₂ alkylphenyl, hydrogen, s is a number from 2 to 100, t is a number from 0 to 1000 and y is a number from 1 to 3 They have a number-average molecular weight preferably ranging from 5,000 to 300,000, more preferably from 8,000 to 200,000 and more particularly from 9,000 to 40,000

According to the present invention, the grafted silicone polymer (s), with a polysiloxane skeleton grafted with non-silicoπed organic monomers comprise a main silicone chain (or polysiloxane (≡Sι-O-) _n ) on which is grafted, inside of said chain as well as possibly at least one of its ends, at least one organic group not comprising silicone The polymers with a polysiloxane backbone grafted with non-silicone organic monomers according to the invention can be existing commercial products, or can also be obtained by any means known to those skilled in the art, in particular by reaction between (i) a starting silicone correctly functionalized on one or more of these silicon atoms and

(n) a non-silicone organic compound itself properly functionalized by a function which is capable of reacting with the functional group (s) carried by said silicone by forming a covalent bond, a classic example of such a reaction is the reaction hydrosylilation between ≡Sι-H groups and vmylic groups CH ₂ = CH-, or else the reaction between thio-functional groups -SH with these same vinyl groups

Examples of polymers with a polysiloxane backbone grafted with non-silicone organic monomers suitable for the implementation of the present invention, as well as their particular mode of preparation, are in particular described in patent applications EP-A-0582152, WO 93 / 23009 and WO 95/03776, the teachings of which are fully included in the present description by way of non-limiting references

According to a particularly preferred embodiment of the present invention, the silicone polymer, with a polysiloxane backbone grafted with non-silicone organic monomers, used comprises the result of radical copolymerization between on the one hand at least one nonionic anionic organic monomer -silicon having ethylenic unsaturation and / or a non-silicone hydrophobic organic monomer having ethylenic unsaturation and on the other hand a silicone having in its chain at least one functional group capable of reacting on said ethylenic unsaturations of said non-silicone monomers in forming a covalent bond, in particular thio-functional groups

According to the present invention, said anionic ethylenically unsaturated monomers are preferably chosen, alone or as a mixture, from acids unsaturated, linear or branched carboxylic acids, optionally partially or totally neutralized in the form of a salt, this or these unsaturated carboxylic acids may more particularly be acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and crotonic acid. Suitable salts are especially the alkali, alkaline earth and ammonium salts. It will be noted that, likewise, in the final grafted silicone polymer, the organic group of anionic nature which comprises the result of the (homo) radical polymerization of at least one anionic monomer of the unsaturated carboxylic acid type can be, after reaction, post-neutralized with a base (soda, ammonia, ...) to bring it in the form of a salt.

According to the present invention, the hydrophobic ethylenically unsaturated monomers are preferably chosen, alone or as a mixture, from acrylic acid alkanol esters and / or methacrylic acid esters from alkanols. The alkanols are preferably in Cι-C ₁₈ and more particularly in Cι-Cι ₂ . The preferred monomers are chosen from the group consisting of isooctyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) isopentyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acτylate, methyl (meth) acrylate, tert-butyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate or mixtures thereof.

A family of silicone polymers with a polysiloxane backbone grafted with non-silicone organic monomers which are particularly suitable for the implementation of the present invention consists of silicone polymers comprising in their structure the following unit of formula (I):

(-Si - O-) _a (- Si -0-) _b (- Si -o -) _c

(G ₂ ) - SG ₃ G, (G ^ -SG, _{(| v)}

in which the Gi radicals, identical or different, represent hydrogen or a C1-C10 alkyl radical or also a phenyl radical; the radicals G ₂ , identical or different, represent an alkylene group in

; G ₃ represents a polymer residue resulting from r (homo) polymerization of at least one anionic monomer containing ethylenic unsaturation; G ₄ represents a polymer residue resulting from r (homo) polymerization of at least one hydrophobic ethylenically unsaturated monomer; m and n are 0 or 1; a is an integer ranging from 0 and 50; b is an integer which can be between 10 and 350, c is an integer ranging from 0 to 50; provided that one of the parameters a and c is different from 0.

Preferably, the motif of formula (IV) above has at least one, and even more preferably all, of the following characteristics:

- the radicals d denote an alkyl radical, preferably the methyl radical;

- n is not zero, and the radicals G ₂ represent a divalent radical in d-Ca, preferably a propylene radical;

- G ₃ represents a polymer radical resulting from the (homo) polymerization of at least one monomer of the carboxylic acid type with ethylenic unsaturation, preferably acrylic acid and / or methacrylic acid;

- G ₄ represents a polymer radical resulting from the (homo) polymerization of at least one monomer of the (meth) acrylate (Cι-Cιo) type, preferably ie (meth) isobutyl or methyl acrylate.

Examples of grafted silicone polymers corresponding to formula (IV) are in particular polydimethylsiloxanes (PDMS) on which are grafted, via a connecting link of thiopropylene type, mixed polymer units of the poly (meth) acid type acrylic and poly (meth) acrylate type.

Other examples of grafted silicone polymers corresponding to formula (IV) are in particular polydimethylsiloxanes (PDMS) onto which are grafted, poly (meth) type polymer units, via a thiopropylene-type connecting link isobutyl acrylate. Preferably, the number-average molecular mass of the silicone polymers with a polysiloxane backbone grafted with non-silicone organic monomers of the invention varies from 10,000 to 1,000,000 approximately, and even more preferably from 10,000 to 100,000 approximately

The silicone graft polymers of the invention are preferably used in an amount ranging from 0.01 to 20% by weight of the total weight of the composition

More preferably, this amount varies from 0.1 to 15% by weight and even more preferably from 0.5 to 10% by weight

The grafted silicone polymers of the invention can be dissolved in the aqueous medium of the aerosol lacquer or used in the form of an aqueous dispersion of particles.

The compositions according to the invention preferably contain from 45 to 100% of water relative to the total weight of the composition in the aerosol and more particularly from 60 to 99.5% of water.

The organic solvents which can be used in the aerosol compositions of the invention are preferably chosen from C-ι-C ₄ alcohols such as, for example, ethanol, isopropanol.

The organic solvents are present in the aerosol compositions in concentrations preferably ranging up to 10% by weight relative to the total weight of the composition in the aerosol and more particularly up to 5% by weight The case corresponding to the absence total organic solvent is particularly advantageous

The compositions according to the invention, packaged in aerosol form in order to obtain a lacquer, comprise a propellant which can be chosen from the group consisting of volatile hydrocarbons such as n-butane, propane, isobutane , pentane, chlorinated and / or fluorinated hydrocarbons and their mixtures The gas can also be used as a propellant carbon dioxide, nitrous oxide, dimethyl ether, nitrogen, compressed air and mixtures thereof Dimethyl ether is particularly preferred

The concentration of the propellant in the aerosol device depends on the nature of the propellant chosen. It is used in the aerosol compositions of the invention in concentrations preferably ranging from 10 to 68% by weight relative to the total weight of the composition in the aerosol device and more particularly from 25 to 50% by weight

The concentration of volatile organic compound (VOC) in a composition according to the invention packaged as an aerosol is preferably less than or equal to 55% by weight relative to the total weight of the formulation packaged as an aerosol

The pH of the compositions according to the invention is generally between 2 and 9 and in particular between 3 and 8 It can be adjusted to the value chosen by means of alkanizing or acidifying agents usually used in cosmetics

The hair compositions in accordance with the invention may contain, in addition to conventional cosmetic additives such as preservatives, softeners, sequestrants, perfumes, viscosity modifiers, pearlescent agents, hydrating agents, anti-dandruff agents, anti-agents -sborborheic, sun filters, conditioning agents for the hair, antioxidants, proteins, vitamins, silicones, polymers In particular, the compositions of the invention can contain in addition styling polymers with properties of hair fixation, anionic, cationic, amphoteric or non-ionic

One of the advantages of the compositions according to the invention compared with the aqueous aerosol lacquers of the prior art containing silicone grafted polymers is that they can be free of any surfactant The compositions according to the invention as defined above can be used as a styling product for shaping and / or maintaining the hairstyle and / or for conditioning the hair.

Another object of the invention consists in a non-therapeutic process for shaping and / or maintaining the hair and / or for conditioning the hair, characterized in that it consists in applying directly to the hair a composition such as previously defined.

The examples which follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLE 1 Aerosol lacquer with 55% VOC (Volatile Organic Compound)

- Grafted silicone polymer of formula (IV) of polymethyl / methylsiloxane structure with propyl thio-3 polymethacrylic acid groups and propyl thio-3 methyl polymethacrylate groups 5 g in MA

- Aminomethylpropanol 100% neutralization qs - Ethanol 20 g

- Demineralized water 40 g

- Dimethylether 35 g

EXAMPLE 2 30% VOC aerosol lacquer

- Grafted silicone polymer of formula (IV) of polymethyl / methylsiloxane structure with propyl thio-3 polymethacrylic acid groups and propyl thio-3 polymethyl methacrylate groups 7 g in MA - Aminomethylpropanol 100% neutralization qs

- Demineralized water 63 g

- Dimethylether 30 g EXAMPLE 3 55% VOC aerosol lacquer

- grafted silicone polymer of structure (1) as defined below 3 g in MA

- Aminomethylpropanol qs

- Ethanol 17 g

- Demineralized water 42 g

- Dimethylether 38 g

Structure (1):

Copolymer obtained by radical polymerization from the mixture of monomers consisting of: a) 60% by weight of tert-butyl acrylate; b) 20% by weight of acrylic acid; c) 20% by weight of silicone macromer of formula:

O CH, II CH CH, CH, = C -C - O - (CH), - Si - O Si -OkSi - (CH), - CH

CH, CH CH CH, n with n being a number chosen such that the number average molecular weight of the macromer is between approximately 9,000 and 12,000; the weight percentages being calculated relative to the total weight of the monomers.

COMPARATIVE EXAMPLES

We compare the 4 formulations of aerosol water lacquers A, B, C, and D defined in the following table:

A sensory evaluation test was carried out on a panel of 5 people. We study for each aerosol lacquer A, B, C and D, as a cosmetic criterion the lacquering power on the hair after application and drying, the powdering effect after detangling fixed hair, the shine after detangling.

Is carried out, with each lacquer tested, a spraying for 10 s on a sample of hair strands of 5 g laid out in a fan on a support.

The 5 people interviewed estimated that the compositions B, C and D according to the invention containing more than 40% by weight of water and at most 25% by weight of organic solvent had better lacquering power, better gloss and an effect less dust compared to composition A according to the prior art containing more than 25% by weight of organic solvent (47%). In addition, lacquer A leads after spraying to white traces on the hair on drying (foaming effect) unlike compositions B, C and

D of the invention.

Claims

1 Aqueous composition for the treatment of keratmic matter, packaged in an aerosol device, producing a lacquer at the outlet of said device, characterized in that it comprises

(a) at least one grafted silicone polymer comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer, the other being grafted onto said main chain, ( b) at least 30% by weight of water,

(c) at least one propellant,

2 Composition according to Claim 1, characterized in that the grafted silicone polymer is chosen from the group consisting of polymers with a non-silicone organic skeleton grafted with monomers containing a polysiloxane, polymers with a polysiloxane skeleton grafted with non-organic monomers -silicon and mixtures thereof

3 Composition according to claim 1 or 2, characterized in that it contains at least one grafted silicone polymer, with non-silicone organic skeleton, consisting of an organic main chain formed from organic monomers not containing silicone, on which is grafted, inside said chain as well as possibly at at least one of its ends, at least one polysiloxane macromer

4 Composition according to Claim 3, characterized in that the non-silicone organic monomers constituting the main chain of the grafted silicone polymer are chosen from the group consisting of ethylenically unsaturated monomers which can be polymerized by the radical route, polycondensation polymerizable monomers, ring opening monomers

5 Composition according to any one of claims 1 to 4, characterized in that it contains at least one silicone graft copolymer comprising

a) from 0 to 98% by weight of at least one lipophilic monomer (A) of low polarity with ethylenic unsaturation of low polarity, free-polymerizable, b) from 0 to 98% by weight of at least one monomer ( B) polar hydrophilic ethylenically unsaturated, copolyméπsable with the monomer (s) of the type

(A), c) from 0.01 to 50% by weight of at least one polysiloxane macromer (C) of general formula

or

X denotes a vinyl group copolymeric with the monomers (A) and

(B),

Y denotes a divalent linking group, R denotes a hydrogen, a Cι-C ₆ alkyl or alkoxy, a C ₆ -Cι ₂ aryl,

Z denotes a monovalent polysiloxane unit having a number average molecular weight of at least 500, n is 0 or 1 and m is an integer ranging from 1 to 3, the percentages being calculated relative to the total weight of the monomers (A), (B) and (C)

6 Composition according to Claim 5, characterized in that the lipophilic monomers (A) are chosen from the group consisting of acrylic or methacrylic acid esters of Crds alcohols, styrene, polystyrene macromers, acetate of vinyl, vinyl propionate, alpha-methylstyrene, tert-butylstyrene, butadiene, cyclohexadiene, cyclohexadiene, ethylene, propylene, vinyltoluene, esters of acrylic or methacrylic acid and 1, 1 -dιhydroperfluoroalcanol or its counterparts, esters of acrylic or methacrylic acid and omega- hydrydofluoroalkanol, esters of acrylic or methacrylic acid and fluoroalkylsulfoamido alcohol, esters of acrylic or methacrylic acid and fluoroalkyl alcohols, esters of acrylic or methacrylic acid and fluoroethers of alcohols, or mixtures thereof

7 Composition according to Claim 6, characterized in that the lipophilic monomers (A) are chosen from the group consisting of n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tertio methacrylate -butyl, 2-ethylhexyl methacrylate, methyl meth acrylate, 2- (N-methyl perfluorooctane sulfonamιdo) -ethylacrylate, 2- (butylperfluorooctaπe sulfonamιdo) -ethylacrylate

8 Composition according to any one of Claims 5 to 7, characterized in that the polar monomers (B) are chosen from the group consisting of acrylic acid, methacrylic acid, N, N-dιmethyl-acrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, (meth) acrylamide, Nt-butylacrylamide, maleic acid, maleic anhydride and their half-esters, hydroxyalkylated (meth) acrylates, diallyidimethylammonium chloride, vinylpyrrolid , vinyl ethers, maleimides, vinylpyπdine, vmylimidazole, polar heterocyclic vinyl compounds, styrene sulfonate, allyl alcohol vinyl alcohol, ie vmylcaprolactam or mixtures thereof

9 Composition according to Claim 8, characterized in that the polar monomers (B) are chosen from the group consisting of acrylic acid, N, N-methylacrylamide, dimethylaminoethyl methacrylate, dimethylaminoethyl quaternized methacrylate, vinylpyrrolidone , and their mixtures

10 Composition according to any one of claims 5 to 9, characterized in that the polysiloxane macromer (C) corresponds to the following general formula (II) O CH,

II

CHR: CR- -c- "(CH 2 ₃ ) ', q ^• (O) - Sι (R ^J ) 3 m - (- O -S. -) - R ⁴

CK (II) in which

R ¹ is hydrogen or -COOH, R ² is hydrogen, methyl or -CH ₂ COOH, R ³ is Cι-C ₆ alkyl, alkoxy or alkylamino, C ₆ -Cι ₂ aryl or hydroxyl, R ⁴ is alkyl, alkoxy or Cι-C ₆ alkylamino, C ₆ -Cι ₂ aryl or hydroxyl, q is an integer from 2 to 6, p is 0 or 1, r is an integer from 5 to 700, m is an integer ranging from 1 at 3

1 1 Composition according to any one of claims 5 to 10, characterized in that the polysiloxane macromer (C) corresponds to the following general formula

with n being a number ranging from 5 to 700

12 Composition according to any one of claims 1 to 11, characterized in that it contains at least one copolymer capable of being obtained by radical polymerization from the mixture of monomers consisting of a) 60% by weight of acrylate tert-butyl, b) 20% by weight of acrylic acid, c) 20% by weight of silicone macromer of formula

with n being a number ranging from 5 to 700; the weight percentages being calculated relative to the total weight of the monomers.

13. Composition according to any one of claims 1 to 1 1, characterized in that it contains at least one copolymer capable of being obtained by radical polymerization from the mixture of monomers consisting of: a) 80% by weight tert-butyl acrylate; b) 20% by weight of silicone macromer of formula:

14. Composition according to any one of claims 5 to 13, characterized in that the polymer with a non-silicone organic skeleton grafted with monomers containing a polysiloxane has a number average molecular weight ranging from 10,000 to 2,000,000 and a glass transition temperature Tg or a crystalline melting temperature Tm of at least - 20 ° C.

15. Composition according to any one of claims 1 to 4, characterized in that it contains at least one polymer with a non-silicone organic skeleton grafted with monomers containing a polysiloxane, capable of being obtained by reactive extrusion of a polysiloxane macromer having a terminal reactive function on a polymer of the polyolefin type comprising reactive groups capable of reacting with the terminal reactive function of the polysiloxane macromer to form a covalent bond allowing the grafting of the silicone onto the main chain of the polyolefin

16 Composition according to Claim 15, characterized in that the reactive polyolefin is chosen from the group consisting of polyethylenes or polymers of monomers derived from ethylene comprising reactive functions capable of reacting with the terminal function of the polysiloxane macromer

17 Composition according to Claim 15 or 16, characterized in that the reactive polyolefin is chosen from the group consisting of copolymers of ethylene or of derivatives of ethylene and of monomers chosen from those comprising a carboxylic function, those comprising a function acid anhydride, those comprising an acid chloride function, those comprising an ester function, those comprising an isocyanate function

18 Composition according to any one of claims 15 to 17, characterized in that the polysiloxane macromer is a polysiloxane comprising a functionalized group, at the end of the polysiloxane chain or near the end of said chain, chosen from the group consisting by alcohols, thiols, epoxies, primary and secondary amines

19 Composition according to any one of claims 15 to 18, characterized in that the polysiloxane macromer is a polysiloxane corresponding to the general formula (III)

T- (CH ₂ ) _s -Sι - [- (OSιR ⁵ R ⁶ ) _r R ⁷ ] _y (III) in which T is chosen from the group consisting of NH2, NHR ', an epoxy function, OH, SH, R ⁵ , R ⁶ , R ⁷ and R ', independently, denote a Cι-C ₆ alkyl, phenyl, benzyl, or C ₆ -C ₁₂ alkylphenyl, hydrogen, s is a number from 2 to 100, t is a number from 0 to 1000 and y is a number from 1 to 3

20 Composition according to claim 1 or 2, characterized in that it contains at least one grafted silicone polymer, with a polysiloxane backbone grafted with non-silicone organic monomers, comprising a main chain of polysiloxane on which is grafted, at l inside said chain as well as possibly at at least one of its ends, at least one organic group not comprising silicone

21 Composition according to Claim 20, characterized in that the polymer with a polysiloxane backbone grafted with non-silicone organic monomers is capable of being obtained by radical copolymerization between on the one hand at least one non-silicone anionic organic monomer having a ethylenic unsaturation and / or a non-silicone hydrophobic organic monomer having an ethylenic msaturatioπ and on the other hand a polysiloxane having in its chain at least one functional group capable of reacting on said ethylenic unsaturations of said non-silicone monomers

22 Composition according to Claim 21, characterized in that the anionic organic monomer containing ethylenic unsaturation is chosen, alone or in the form of a mixture of monomers, from linear or branched unsaturated carboxylic acids

23 Composition according to Claim 22, characterized in that the anionic organic monomer containing ethylenic unsaturation is chosen, alone or in the form of a mixture of monomers, from acrylic acid, methacrylic acid, maleic acid, anhydride maleic, itaconic acid, fumanic acid and crotonic acid or their alkali, alkaline earth or ammonium salts, or mixtures thereof

24 Composition according to Claim 22, characterized in that the hydrophobic organic monomer containing ethylenic unsaturation is chosen, alone or as a mixture of monomers, from acrylic acid esters of alkanol and / or the methacrylic acid esters of alkanol, preferably the alkanol being in d-

C _{l £}

25 Composition according to Claim 24, characterized in that the hydrophobic organic monomer with ethylenic iπsaturation is chosen, alone or as mixtures of monomers from the group consisting of isooctyl (meth) acrylate, isononyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isopentyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) methyl acrylate, tert-butyl (meth) acrylate, tπdecyl (meth) acrylate, stearyl (meth) acrylate

26 Composition according to any one of claims 20 to 25, characterized in that the grafted silicone polymer comprises on the main silicone chain, at least one organic group of anionic nature obtained by r (homo) radical polyméπsatιon of at least one anionic monomer of the unsaturated carboxylic acid type, partially or totally neutralized in the form of a salt

27 Composition according to any one of claims 20 to 26, characterized in that the grafted silicone polymer is chosen from silicone polymers comprising in their structure the unit of formula (IV) below

(-If - O -) _a (- Sι-0-) _b (-Sι -o—) _c

(G ₂ ) - SG ₃ G, (G ₂ ) _m - SG _{4 (} ^

in which the radicals d, identical or different, represent hydrogen or a Cι-C ₁₀ alkyl radical or else a phenyl radical, the radicals G ₂ , identical or different, represent represents a Cι-C ₁₀ alkylene group, G ₃ represents a polymer residue resulting from the (homo) polymerization of at least one anionic monomer containing ethylenic unsaturation, G ₄ represents a polymer residue resulting from the (homo) polyméπsatιon of minus one hydrophobic ethylenically unsaturated monomer, m and n are equal to 0 or 1, a is an integer ranging from 0 and 50, b is an integer which can be between 10 and 350, c is an integer ranging from 0 and 50, provided that one of the parameters a and c is different from 0

28 Composition according to Claim 27, characterized in that the unit of formula (IV) has at least one of the following characteristics

the radicals d denote a Cι-C ₁₀ alkyl radical,

- n is not zero, and the radicals G ₂ represent a divalent C ₁ -C ₃ radical, - G ₃ represents a polymer radical resulting from r (homo) polyméπsatιon of at least one monomer of the carboxylic acid type with ethylenic unsaturation,

- G ₄ represents a polymer radical resulting from the (homo) polymerization of at least one monomer of the (meth) alkyl acrylate type (C1-C10)

29 Composition according to Claim 27 or 28, characterized in that the unit of formula (IV) simultaneously has the following characteristics

the radicals d denote a methyl radical,

- n is not zero, and the radicals G ₂ represent a propylene radical,

- G ₃ represents a polymer radical resulting from the (homo) polymérιsatιon of at least acrylic acid and / or methacrylic acid,

- G ₄ represents a polymeric radical resulting from the (homo) polymerization of at least one monomer of the (meth) acrylate or isobuylate type

30 Composition according to any one of claims 20 to 29, characterized in that the number-average molecular mass of the polymer with a polysiloxane backbone grafted with non-silicone organic monomers varies from 10,000 to 1,000,000 approximately, and even more preferably from 10,000 to 100,000 approximately

31 Composition according to any one of claims 1 to 30, characterized in that the grafted silicone polymer (s) are used in an amount ranging from 0.01 to 20% by weight relative to the total weight of the composition and preferably from 0.1 to 15% by weight and even more preferably from 0.5 to 10% by weight

32 Composition according to any one of Claims 1 to 31, characterized in that it contains from 45 to 100% water relative to the total weight of the composition in the aerosol and more preferably from 60 to 99.5 % water

33 Composition according to any one of claims 1 to 32, characterized in that the organic solvent is chosen from alcohols in

Cι-C ₄

34 Composition according to any one of claims 1 to 33, characterized in that it contains from 0 to 10% of organic solvent relative to the total weight of the composition in the aerosol and more preferably from 0 to 5% of organic solvent

35 Composition according to any one of claims 1 to 34, characterized in that it does not contain an organic solvent

36 Composition according to any one of claims 1 to 35, characterized in that the propellant is chosen from the group consisting of volatile hydrocarbons, chlorinated and / or fluorinated hydrocarbons and their mixtures, carbon dioxide, protoxide nitrogen, dimethyl ether, nitrogen, compressed air and mixtures thereof

37 Composition according to any one of claims 1 to 36, characterized in that the propellant is dimethyl ether

38 Composition according to any one of claims 1 to 37, characterized in that the propellant is present in concentrations preferably ranging from 10 to 68% by weight relative to the weight total of the composition in the aerosol device and more particularly ranging from 25 to 50% by weight

39 Composition according to any one of claims 1 to 38, characterized in that the concentration of volatile organic compound

(VOC) is less than or equal to 55% by weight relative to the total weight of the composition packaged in aerosol

40 Composition according to any one of claims 1 to 39, characterized in that the pH varies from 2 to 9 and in particular from 3 to 8

41 Composition according to any one of claims 1 to 40, characterized in that it additionally contains a conventional cosmetic additive chosen from the group consisting of preservatives, softeners, sequestrants, perfumes, viscosity modifiers, pearlescent agents, moisturizing agents, dandruff agents, anti-seborrheic agents, sun filters, hair conditioning agents, antioxidants, proteins, vitamins, silicones, alkalizing or acidifying agents for polymers anionic, cationic, amphoteric or nonionic styling with fixing properties of the hair, their mixtures

42 Composition according to any one of claims 1 to 41, characterized in that the grafted silicone polymer is dissolved in the aqueous medium of the composition or used in the form of an aqueous dispersion of particles

43 Composition according to any one of claims 1 to 42, characterized in that the keratmic materials are human hair

44. Composition according to any one of claims 1 to 43, characterized in that it is a hair product for maintaining and / or shaping the hair and / or for conditioning the hair.

45. Non-therapeutic process for maintaining and / or shaping the hair and / or conditioning the hair, characterized in that it consists in applying to the hair a composition as defined according to any one of claims 1 to 44.